JPS5923859B2 - Method for producing extruded catalyst particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst manufacturing process to provide an improved hydrocarbon conversion catalyst.

The present invention relates to a method for increasing the pore size of catalysts supported on refractory inorganic oxides.

Catalysts prepared by the process of the present invention are particularly useful in the hydrorefining of petroleum crude oils and in the hydrorefining of residual oils recovered as bottoms during distillation of petroleum crude oils.

This residual oil can be used as asphaltene oil, liquid asphalt,
It goes by many names, including fish oil, tailings, residual oil, residual prefix crude oil, and bunker fuel oil.

Petroleum crude oils and residual oils typically contain nitrogen-containing compounds, sulfur-containing compounds and heptane-insoluble asphaltenes, which alone or in combination can
The conversion of the oil to lower boiling, more useful fractions is significantly inhibited.

Nitrogen- and sulfur-containing compounds are reduced to an acceptable extent under hydrorefining conditions and converted to ammonia and hydrogen sulfide, which are easily separated as gaseous products.

However, the reduction of heptane-insoluble asphaltenes is substantially more difficult.

These compounds tend to deposit on the catalyst provided in the reaction zone, forming a gummy hydrocarbon residue, which acts as a coke precursor.

Since the deposition of such residues results in significant losses of product, it is economically desirable to convert such asphaltones into useful hydrocarbon fractions.

The significance of the pore volume-pore diameter characteristics of catalysts for the hydrorefining of crude oils and residual oils, and especially for the conversion of heptane-insoluble asphaltenes, is shown in U.S. Pat. No. 3,666.
It is clear from No. 6,685.

That is, the total pore volume of pores with an average pore diameter of 100 to 500 Å is at least 0.4 CC.
/f was disclosed to be a particularly effective catalyst for the conversion of heptane-insoluble asphaltenes.

The object of the present invention is to provide a new method for producing catalysts.

A further particular object is to provide a method for increasing the macropore volume of catalysts supported on refractory inorganic oxides.

Here, macropores refer to pores having an average diameter exceeding about 100 angstroms as measured by mercury porosity.

The present invention generally involves mixing a powdered refractory inorganic oxide with a binder-lubricant, further adding a peptizer and a water-soluble surfactant, extruding the resulting tow, and producing an extrudate. This embodies a catalyst manufacturing method that consists of drying and power firing.

Other objects and embodiments of the invention will become apparent from the detailed description below.

According to the method of the invention, the powdered refractory inorganic oxide is first mixed with a binder, which also acts as a lubricant in the subsequent extrusion step.

Such binder-lubricants are well known in the art and include starch, polyvinyl alcohol, methylcellulose, graphite, micropolyethylene, and the like.

Suitably, the powdered refractory inorganic oxide is mixed with about 0.01 to 5% by weight binder-lubricant.

The refractory inorganic oxide referred to herein includes not only synthetic refractory inorganic oxides but also natural ones.

Suitable refractory inorganic oxides include alumina, silica,
Zirconia, doria, boria, and the like, and complexes thereof, e.g. alumina-silica, alumina-
There are zirconia etc.

Alumina is a preferred refractory inorganic oxide, especially for hydrorefining of crude oils and residual oils as in the present invention.

The alumina used in the preparation of the catalyst according to the invention can be various water-use alumina oxides or alumina gels, such as boehmite, gibbsite, etc.
e), bayerite, etc.

It is also possible to use alpha alumina monohydrate of boehmite structure, which is obtained as a by-product of alcohol production by hydrolysis of aluminum alcoholates, ie aluminum alkoxides.

Particularly suitable are aluminas that have been thermally treated, for example at temperatures above about 400° C., to remove at least a portion of the normally found chemically and/or physically bound water and hydroxyl groups.

Preferably, the alumina has a surface area of about 100 to 500
m7S' activated aluminas, particularly gamma and eta aluminas obtained by thermal treatment at temperatures in the range of about 400-850°C.

Peptizers useful in the present invention are those commonly known in the art for converting gel materials back into sol form.

Therefore, as this peptizer, water or
There are weak acids such as formic acid, acetic acid, and propionic acid.

Strong acids such as sulfuric acid, saline acid, nitric acid, etc. substantially cancel out the beneficial effects of surfactants and are therefore not suitable for use in the present invention.

Water is the preferred peptizer. In either case, only a sufficient amount of veptizer is used to convert the gel back into a soft plastic, but not enough to completely convert the gel into a sol.

Peptizer is suitable for mechanical loss; put the gel in a stirrer,
The veptizer and surfactant may be incorporated into the powdered refractory inorganic oxide gel with the surfactant by adding the veptizer and surfactant during the mixing operation.

Although various surfactants are useful in the process of the present invention, they include anionic, cationic, and nonionic surfactants that are harmful to the catalyst produced for its purpose (application). It leaves no residue.

Suitable surfactants include 03-C1□ alcohols;
Linear primary alcohol production compounds, dimethyl silicones, silicone polyether copolymers, and various well-known polyoxyethylene alkylphenols, polyoxyethylene esters of fatty acids, polyoxyethylene alcohols, polyoxyethylene mercaptans ,
There are polyoxyethylene alkylamines, polyoxyethylene alkylamides, and the like.

Linear primary alcohol polyether, commercially available under the trade name rAntarox BL-240J, is a particularly suitable surfactant.

Preferably, the surfactant is utilized in a range of about 0.1-10.0% by weight of the refractory inorganic oxide hydrogel.

The extrusion operation in the present invention is suitably carried out using commercial extrusion equipment.

For example, tow is processed continuously in a cylinder by a rotating screw and extruded through a die with a number of openings of appropriate diameter to obtain an extruded product of the desired size.

The tow is continuously extruded through the die at a pressure of at least about 150 pSig and cut into particles of desired length by a rotating knife.

After the tow is extruded, the extruded product is dried and calcined.

Drying is typically carried out at temperatures up to about 200°C for about 1 to 24 hours.

Power firing is preferably carried out at a temperature of about 350 DEG to 850 DEG C. under an oxidizing atmosphere, such as in air, and suitably for a period of 2 to 4 hours.

Hydrogen purification catalysts typically contain Part VIB as a catalyst component.
Contains group metals and group VIII metals, and/or their oxides and sulfides.

Of the Group VIB metals, molybdenum, tungsten and chromium, molybdenum is generally preferred.

Group VIII metals, namely iron, nickel, cobalt,
Among platinum, palladium, rhodium, ruthenium, iridium and osmium, nickel is generally preferred.

The above components, such as molybdenum and nickel, or their appropriate precursor compounds (such as molybdic acid and nickel nitrate), may be complexed into the extruded particles by impregnation and/or ion exchange methods.

These catalyst components may be complexed to the starting refractory inorganic oxide prior to mixing the inorganic oxide with the binder-lubricant and subsequent addition of the surfactant and peptizer. .

Alternatively, aqueous solutions of soluble compounds of each of the catalyst components may be mixed, that is, mixed so as to act as the peptizer, and may be composited into the extruded particles.

Alternatively, the catalyst component may be complexed to the extruded particles by an impregnation method and/or an ion exchange method, either before or after the extruded particles are dried and calcined.

However, if a catalyst component or its precursor compound is added to the force-calcined extruded particles, it is necessary to be able to subject the resulting composite to an additional force-calcining treatment.

The following example represents one preferred embodiment of the invention and is not intended to unduly limit the general broad scope of the invention as claimed.

Example 1 In this example, extruded catalyst particles were produced by the method of the present invention.

Finely powdered alpha alumina monohydrate was mixed with about 2% by weight of methylcellulose as a binder-lubricant.

Add a sufficient amount of water to the mixture as a peptizer,
A smooth extruded tow was obtained.

The above water is used as a surfactant.
It contained 2 grams of -240.

The surfactant, or detergent, was a linear primary alcohol polyether.

The resulting mixture was kneaded for about 30 minutes, then 150
psig; Extruded under pressure, after drying, is 50℃
Extruded particles having a diameter of 1/3'2 to 1/8 inch were obtained by firing at a temperature of .

This extruded product is hereinafter referred to as catalyst A. Example 2 In this example, extruded particles were prepared in substantially the same manner as in Example 1, except that the binder-oil lubricant described above was not added.

That is, add a sufficient amount of water to powdered alpha alumina.
In addition to the hydrate, a homogeneous extruded tow was obtained.

The above water contains Antarox B L as a surfactant.
It contained about 10% by weight of -240.

The resulting mixture was extruded at a pressure of 150 psig and, after drying, was calcined at a temperature of 50°C to a diameter of 1/32~
1/8 inch extruded particles were obtained.

This extruded product is hereinafter referred to as catalyst B. Example 3 In this example, extruded particles were prepared in substantially the same manner as in Example 1, but the above-mentioned surfactant was omitted.

That is, finely powdered alpha alumina monohydrate was mixed with about 2% by weight of methylcellulose as a binder-lubricant.

A sufficient amount of water was added to the above mixture using a peptizer to form a homogeneous extruded tow.

The resulting tow was extruded at a pressure of 150 psig, dried, and then calcined at a temperature of 50°C to a diameter of 1/32.
~1/8 inch extruded particles were obtained.

This extruded product is hereinafter referred to as catalyst C.

Example 4 In this example, extruded particles were prepared in substantially the same manner as in Example 1, except that not only the binder-lubricant described above but also the surfactant were omitted.

That is, a sufficient amount of water was added to powder A: Rufa alumina monohydrate to obtain a homogeneous extruded tow.

The obtained tow was extruded at a pressure of 150 psig, and after drying, it was calcined at a temperature of 50°C to a diameter of 1/32.
This extruded product, which yielded ~1/8 inch extruded particles, is hereinafter referred to as Catalyst D.

Table 1 below shows the catalyst A obtained by the method according to the present invention.
and Catalysts B, C and D, which omit the novel combination of binder-lubricant and surfactant.

As can be seen from the results in Table 1, the pore size of the extruded particles prepared by the method of the present invention with the combination of binder-lubricant and surfactant is the same as that of extruded particles using only surfactant (112 extruded particles with binder-lubricant only (93 Å), or extruded particles with neither binder-lubricant (111 Å)
(13 angstroms)
0 angstrom).

Furthermore, the macropore volume of catalyst A is at least twice as large as that of either catalysts B, C or D.

Claims (1)

[Scope of Claims] 1. The total pore volume of pores having an average pore diameter of 100 to 500 angstroms is at least O per gram,
4 = A method for producing extruded catalyst particles having: a) mixing a powdered refractory inorganic oxide and a binder-lubricant, wherein the binder-lubricant is 0.01% of the refractory inorganic oxide; b) addition of a peptizer; C) 0.1 to 10% based on the weight of the refractory inorganic oxide;
d) extrude the resulting dough; and e) dry and bake the extrudate. A method for producing extruded catalyst particles, consisting of each step.